Metal-free catalytic hydrogen production from a polymethylhydrosilane–water mixture

Abstract

Hydrogen gas is the most promising carbon-free energy carrier although its on-demand generation remains a formidable challenge.

Wettability-Driven Palladium Catalysis for Enhanced Dehydrogenative Coupling of Organosilanes

“…In this case, the recovered Pd/XC-72-700-Ar material was reused at least 10 times while maintaining its initial activity (i.e., the total turnover number (TON) approached 8.0 × 10 5 ; Figure S5 in the Supporting Information). To the best of our knowledge, this result is far superior to any reported example of the hydrolytic oxidation of organosilanes (Table S8 in the Supporting Information). , …”

“…However, with the aim of maximizing the efficiency of organosilanes as DCC reagents, the inherently sluggish kinetics for Si–H cleavage must be circumvented . While several efficient homogeneous catalysts have been developed, the corresponding heterogeneous catalysts have generally displayed significantly lower efficiencies despite the large number of attempts . With the aim of overcoming these issues, highly robust solid catalysts able to significantly improve the reaction kinetics under moderate conditions are thus urgently required.…”

Interactions of hydrosiloxane and vinylsiloxane groups with aluminum oxide surfaces

“…However, since water is present in excess at ambient conditions compared with Si─H groups, reactions with water cannot be excluded. As was shown before with catalytic amounts of hydroxide ions, the reaction rate of hydrosiloxanes is zero order with respect to water, which can be explained by a rate‐determining step for the activation of PMHS . Nevertheless, the acid‐base properties of the surface have an important influence on the reactions.…”

“…Furthermore, electrophilic addition reactions to alkenes in the presence of acids are known . In the case of hydrosiloxanes, reactivity under acidic or basic conditions is known. Under catalysis, hydrosiloxanes can react with protic hydrogen under release of hydrogen gas.…”

Pd, Rh and Ru nanohybrid-catalyzed tetramethyldisiloxane hydrolysis for H2 generation, nitrophenol reduction and Suzuki–Miyaura cross-coupling

“…[40][41][42] Third, the only by-products, silanols derived from siloxane hydrolysis, are widely used in cross-coupling reactions and silicon-based polymeric building materials. [43][44][45][46][47] Fourth, some siloxanes, e.g. tetramethyldisiloxane (TMDSO), constitute silicone industrial refuse and need plenty of manpower and materials to degrade them.…”